Method of polymerizing nonwrin



Patented Nov. 7, 1950 METHOD OF POLYMERIZING NONWRIN- KLING OILS TO WRINKLING OILS Gordon M. Williams, Glens Falls, N. Y., assignor to New Wrinkle, Inc., Dayton, Ohio, a corporation of Delaware No Drawing. Original application May 6, 1943,

Serial No. 485,897. Divided and this application April 9, 1947, Serial No. 740,477

11 Claims.

This invention relates to drying oils having the property of yielding wrinkle films when compounded with resins and driers to form a varnish and applied to a surface and dried.

This application is a division of my copending application Serial Number 485,897, filed May 6, 1943, being Patent No. 2,482,901, which is a continuation-in-part of application Serial Number 485,646, filed May 4, 1943, being Patent No. 2,431,357.

More particularly, the present invention relates means whereby polymerization nuclei may be initially formed whereby to improve or increase the drying rate and wrinkle forming properties of drying oils by treatment according to the present invention.

In the formation of surface wrinkles on a coating composition it is important that there be developed a considerable degree of strain caused by contraction orexpansion, or both, between the surface layer and the body of the drying film. whn'eme mechanism of drying of coating films is not clearly understood, it is believed to include polymerization (see Bennetts Driers and Drying, page 5 1941, published by Chemical Publishing Company, Brooklyn, New York). Apparently, this contraction or expansion of the surface layer is a condition established by the initial formation of polymerized nuclei on the surface of the coatingfilm' to form a thin skin and the subsequent polymerization of the underlayers. This tends to set up'the required strain and causes the formation of the wrinkle texture or pattern. It is thus apparent that acceleration of therate offormation of polymerized units, first on the surface layer-and finally throughout the coating film, will aid materially in the speedy formation of the wrinkle texture or pattern which is desired. Furthermore, it is reasonable to assume that the more "closely knit the polymerized associations are, the more uniform and pronounced will be the to indicate that polar bodies are first formed by the introduction of oxygen into the points of unsaturation. These polar molecules are then able to polymerize and form nuclei for further polymerization, and this gradual polymerization of polar molecules leads ultimatelyto the hardening of the coating film.

Furthermore, it is understood that the difference in drying characteristics between tung oil (China wood oil) and other oils such as linseed oil is largely due to the fact that the former by virtue of its high degree of conjugation and symmetry is able to form a closely knit three dimensional polymerized nucleus. Linseed oil and other similar oils, on the other hand, form drawn out polymerized units which are comparatively loosely knit.

The present invention deals particularly with means whereby the initial formation of polymerizing nuclei may be established in drying oils which are normally nonwrinkling in order to accelerate their drying rate and to improve and fully develop their wrinkle forming characteristics. This is brought about particularly by the introduction in said oils of organometallic compounds and metallic ions which serve to initiate polymerization and which tend largely to eliminate the necessity for the initial formation of polar bodies by means of oxidation of the oil. For example, linseed oil and soya bean oil are considered to be normally nonwrinkling oils; however, if these one are subjected to blowing they are readily transformed into wrinkling oils and the reason for this transformation is believed to be the formation of polar bodies due to the partial oxidation or the introduction of oxygen in the oil molecules.

By way of illustration and without thereby intending to limit the present invention, there is given below a diagrammatic presentation of the manner in which a small amount of these compounds can initiate polymerization of the oil molecule. The oleic acid radical and a simple organometallio compound are used.

O CH-(CHzh-OH;

to picture the complexity involved when a triglyceride made up of acid radicals containing more than one unsaturated bond is treated with an dfganometallic compound.

The; fundamental principles of the present invention are applicable to the treatment of other esters-or drying oils besides the triglyceride form'ation. Typical of these are those obtained by the reaction "of unsaturated fatty acids with monohydric alcohols and other polyhy iric alcohols 'thantrihydric. These substances possess potential drying properties which may be developeu under proper conditions and which, with the'aid of the polymerizing nucleus which results from the practice of the, present invention will harden and produce suitable films.

Further. by way of illustration, and without thereby intending to limit the present invention, the following examples are given:

EXAMPLE I Csggl lsin ZjQgramsof diethyl ether is added. The

stirrer is started and the contents allowed tq re: act at oo t mp r t .iqrTa pmiiima ly hours. The heat is then increased to approximatlyw50 C. f'or th e removal of'the ether and then to 200C. at which temperature it is held fof'a' period of about i hours until a rather visc'o'us oil"results The nitrogen supply is shut 01f approximately 1 hour prior to the completion of the cook. The resulting product is a viscous oil possessing a highly increased drying rate and wrinkle forming properties which when compounded with resin and driers as iscustomary in the art will produce a coating compositionwhich willyield a well defined uniform wrinkle film. on application and drying. i r 1 EXAMPLE II 100 grams of soya bean oil are placed in a con tainer such as described in Exampl I. A blanket of nitrogen is thrown over the surface of the'oil:

while the latter is heated to a temperature of 120 C. to remove any water which may be present. The oil isthen cooled to 0..C..w-ith an ice and salt mixture and 0.05 gram of sodium added.

The mixture is then allowed to warm up to room temperature with constant stirring. When no fi'irt'hr reaction is evident the oil is heated to lZ Qf C. with constant agitation and under a blanlgetofnitrogen The temperature is: held at this point for approximately 30 minutes. The resulting product -may be utilized: in thecustomary manner for producing a wrinkle fvar nish composition. w

EXAMPLE III a I TolQo gr'ams of sunflower oil 0.15pm or, finely divided copper is added in the inanner.de-. scribed inExample, .II with the-exception that the copper. may e added at room temperature instead of at 0 C. l The oil is then heated to 150,".- ogana held at that temperature for 3 hours with, constant stirring and underf a blanketof 'nitro gen. 1.

The r l produ t i a co sip ;nnqces ing a highly increased drying rate and wrinkle, forming properties which when compounded'with resins'and driers in a'varnish coating compost. tion and applied and dried will exhibit {better drying properties and wrinkling characteristics than similar compositions prepared from the.

untreated oil. 1 v 1 It willbe understood that the foregoing ex'-' amples are illustrative of the application'offthe; method of the present. invention; and that it isj not intended to have the present invention ited to or circumscribed by the particulardetails; oi procedure materials; or apparatus therein set forth or described in 'view of the fact 'that thei present invention is susceptibleto modificatio sf depending on individual preference and coridi-f tions without departing from the spirit of this disclosure and the scope ofthe appended claims, Iclaim: t V 1. The method of treating 'a vegetahle fattyoil' to v n r e. sd yi s ra e an ansiorm'i 'iinto; a wrihkl inig oilwhioh commi sh tins 101) parts. by weight-or sa d on, with 0.15 p it by'weight r, finely dividedfc'opper at a temperatu" of; about, 150 c. in'an inert ambient atmosphere; and. 110m; ing. the temperature of the mixture. at this level for approximately 3 hours. y i

2. ,The In'etliod of trea "soya'bean 611,50

' increase its drymgrate aria transform" minus wrinkling oil which comprises heating parts 2 byweight of saidoil with0.1-5 .part by weight of 3. The method of treating sunflower oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by weight of said oil with 0.15 part by weight of finely divided copper at a temperature of about 150 C. in an inert ambient atmosphere, and holding the temperature of the mixture at this level for approximately 3 hours.

4. The method of treating a vegetable fatty oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by weight of said oil in an inert ambient atmosphere at a temperature of 120 C. to remove water therefrom; cooling the oil to room temperature; adding 0.15 part by weight of finely divided copper; heating the mixture to a temperature of about 150 C. in an inert, ambient atmosphere with constant agitation; and holding the temper ature of the mixture at this level for approximately 3 hours.

5. The method of treating soya bean oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by weight of said oil in an inert ambient atmosphere at a temperature of 120 C. to remove water therefrom; cooling the oil to room temperature; adding 0.15 part by weight of finely divided copper; heating the mixture to a temperature of about 150 C. with constant agitation; and ho1ding the temperature of the mixture at this level for approximately 3 hours.

6. The method of treating sunflower oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by weight of said oil in an inert ambient atmosphere at a temperature of 120 C. to remove water therefrom; cooling the oil to room temperature; adding 0.15 part by weight of finely divided copper; heating the mixture to a temperature of about 150 C. in an inert ambient atmosphere with constant agitation; and holding the temperature of the mixture at this level for approximately 3 hours.

7. The method of making a wrinkling coating composition comprising heating a vegetable fatty oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by weight of said oil with 0.15 part by weight of finely divided copper at a temperature of about 150 C. in an inert atmosphere, holding the temperature of the mixture at this level for approximately 3 hours, and then adding resin and drier.

8. The method of making a wrinkling coating composition comprising treating sunflower oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by weight of said oil with 0.15 part by weight of finely divided copper at a temperature of about 150 C. and then adding resin and drier.

9. The method of making a wrinkling coating composition comprising treating a vegetable fatty oil to increase its drying rate and transform it into a wrinkling oil which comprises heating parts by weight of said oil in an inert ambient atmosphere at a temperature of C. to remove water therefrom; cooling the oil to room temperature; adding 0.15 part by weight of finely divided copper; heating the mixture to a temperature of about C. with constant agitation; and holding the temperature of the mixture at this level for approximately 3 hours, and then adding resin and drier.

10. The method of making a wrinkling coating composition comprising treating soya bean oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by Weight of said oil in an inert ambient atmosphere at a temperature of 120 C. to remove water therefrom; cooling the oil to room temperature; adding 0.15 part by weight of finely divided copper; heating the mixture to a temperature of about 150 C. with constant agitation; and holding the temperature of the mixture at this level for approximately 3 hours, and-then adding resin and drier.

11. The method of making a wrinkling coating composition comprising treating sunflower oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts by weight of said oil in an inert ambient atmosphere at a temperature of 120 C. to remove water therefrom; cooling the oil to room temperature; adding 0.15 part by weight of finely divided copper; heating the mixture to a temperature of about 150 C. with constant agitation; and holding the temperature of the mixture at this level for approximately 3 hours, and then adding resin and drier.

GORDON M. WILLIAMS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,219,862 Bradley Oct. 29, 1940 2,387,424 Waldie Oct. 23, 1945 FOREIGN PATENTS Number Country Date 366,520 Great Britain Feb. 1, 1932 470,498 Great Britain Aug. 16, 1937 

1. THE METHOD OF TREATING A VEGETABLE FATTY OIL TO INCREASE ITS DRYING RATE AND TRANSFORM IT INTO A WRINKLING OIL WHICH COMPRISES HEATING 100 PARTS BY WEIGHT OF SAID OIL WITH 0.15 PART BY WEIGHT OF FINELY DIVIDED COPPER AT A TEMPERATURE OF ABOUT 150*C. INA N INERT AMBIENT ATMOSPHERE, AND HOLDING THE TEMPERATURE OF THE MIXTURE AT THIS LEVEL FOR APPROXIMATELY 3 HOURS. 